Three types of melamine–formaldehyde porous sorbents were synthesized by using the fumed silica as an inorganic template. The changes in polymerization conditions lead to a differentiation of the porosity and surface area of these materials. This synthesis allowed preparing the materials of narrow pore size distributions with pore sizes over the range 2.8–6.8nm, and specific surface areas up to 250m2/g. The analysis of pore structure was based on the comparison of nitrogen adsorption isotherms on a given porous sorbent and a standard nonporous polymer. Additionally the measurements of thermal stability and swelling of synthesized polymers were made. Adsorption of organic substances from aqueous solutions on porous polymers was also investigated.